Water-insoluble azo-dyestuffs and fiber dyed therewith



Patented Aug. 22, 1933,

UNITED STATES WATERJNSOLUBLE AZO-DYESTU I 'FS AND FIBER DIED THEREWITH Franz Henle and Herbert Kracker, Frankfort-onthe-Main-Hochst, Germany, assignors to Gen- I eral Aniline Works, Inc., New York, N. Y., a

, Corporation of Delaware No Drawing. Application April 24, 1931, Serial No. 532,690, and in Germany May 9, 1930 Claims. (01. 260-86) I present invention relates to .new waterinsoluble azo-dyestufis and to fiber dyed therewith.

"We have found that new valuable water-insol-- '9 uble azo-dyestufls are obtainable by combining with a diazotized amine of the benzene, naphthaleneor anthracene-series an aroyl-acetic 801d arylide of the following general formula wherein R. and R stand for radicals of the benaene-, naphthaleneor diphenyl-series the arylide and amine, however, being free from groups which would make the dyestuffs soluble in water, such as the sulfonic acid or carboxylic acid group. i

The dyestufis, thus obtained, yield yellow to red tints and for the greater part have a Very good iastness to light.

The aroyl-acetic acid general formula R-COCH2CONH-R maybe obtained, forinstance, by condensing an aroyl-acetic acid ester of the formula R-'COCH2COOC2H5 with a primary aromatic amine of the iormula Furthermore, we have found that the said arylides'have such an aflinity for cotton fiber that. according to the process hereafter described, dyeings are obtained which, as regards mono arylides of the intensity and beauty of shade, surpass the dye ings obtained with the corresponding acetoacetic-acid-mono-arylides. T

The said arylides, therefore, are useful for developing the dyestufi on the cotton fiber. A large number of the dyeings obtained by developing the said arylides with any diazotized base have a 49 very good tastness to light. Besides, the dyestufls have a very good fastness to water, chlorine and boiling with soap and sodium carbonate.

wherein R. and R stand iorradicals of the benaene-, naphthalene or cliphenyl-series, R" stands for a radical of the benzene-, naphthaleneor antbracene-series, the radicals, however, being free from groups whichwould make the dyev ,stufis soluble in water.

Thefollowing examples serve to illustrate the invention, but they are not intended to limit it thereto: 1 e I Dyeing prescription for Examples 1 and 2f Well boiled cotton fabric is dried and impregnated on the foulard with the groundlng liquor, squeezed and dried. v The dry goods are passed through the diam-solution, exposed to the air for about 3 minutes and passed through a bath containing about 3 cc of hydrochloric acid oi 22 B. per liter. The material is then well' rinsed, soaped in a boiling bath containing soap and sodium carbonate, rinsed again and dried.

EXAMPLE 1 (a) Grounding liquor 16.2 grams of benzoylacetic acid-ortho-chloranilide are made into a paste with cc of Turkey red oil of strength and 21 cc of caustic soda solution of 34 B. This paste is' dissolved by pouring 1 liter of boiling water over it. 7 (b) Diazo-solution 11.4 grams of l-amino-2-methyl-4-nitrobendiazo-solution is rendered neutral'to Congo paper. by means of about 15 grams of crystallized sodium acetate and the whole'is made up to 1 liter.

There is obtained a .vivid,medium yellow of very good fastness to light.

The dyestufi has the following mula . v H I l I probable for- CHI N0: EXAMPLnZ (a) Grounding liquor The grounding liquor is prepared as in Example 1 by using, however, 15 grams oi benzolyacetic acid-ortho-toluidide.

, (b) Dia'zo-solution The dye-bath, likewise, is prepared as in-Ex ample 1 but from 12.6 grams of 1-amino-2- methoxyi-nitrobenzene.

There is obtained a reddish-yellow of ve y good iastness to light. p

The dyestufl! has the following probably for- N V p mo N ocni EXAMPLEB 23.9. grams of benzoylacetic-acid anilide are dissolved in 50 cc of hot ZN-caustic soda'solution and-water and, after cooling, precipitated in a flnelydispersed state by-rneans of 50 cc of. 2N- acetic acid. Into this suspension there is run a diazo-solutionprepared-as follows: 17.3 grams of 1-amino-4-chloro2 nitrobenzene are diazotized in the usual nanner with 27 cc of hydrochloric acid'of 22 B; and 7.2 grams of sodium nitrite. The clear diazo-solution is; rendered neutral to Congo paper by means of sodium ace-' tate.

@Atter stirring for some hours, the formation of "the dyestufi which has the following probable 'i'ormula II N isfinished. It filtered by suction and forms a yellow paste of very good fastness to light.

'EXA-MPYLEY 4 a "15.2 grams of l-amino-2-methyl-4-nitrobenzene are diazotized in the usual manner by means of 80 cc. of hydrochloric acid of 20 B and 7.2 grams of sodium nitrite dissolved in water. The clear diam-solution is rendered neutral to Congo paper by means of sodium acetate. Into this solution, there is man arylide solution prepared by dissolving 27.4 grams of para-chlorobenzoylaceticacid anilide in cc of 2N-caustic soda solution and hot water. v

The dyestufi which is formed precipitates and may be separated by filtering by suction. It has the following probable formula and forms a. yellow paste of verygood fastness to i ht. v r

EXAMPLE v,

(a) Grounding liquor A paste is prepared from 20 gramsof a -naphkey-red oil of 50% strength and 21 cc of caustic soda solution of 34 B. This paste is dissolved by pouring on to it 1 liter of boiling water.

(b) Diazo printing color 12.6 grams of 1-amino-4-nitro-2-methoxybenzene are diazotized by means of 21 cc of hydrochloric acid of 22 B. and 5.6 grams of sodium nitrite dissolved in water, with addition of ice.

The whole is madeup to 500 cc, thickened with 480 grams of tragacanth 1000) and rendered neutral to Congo paper by addition of 20 grams of crystallized sodium acetate.

(0) Printing prescription II N OCH:

By using as coupling components any other aroyl-acetic acid-mono-arylides and "as diazotizing components any other amine, dyestuffs are obtainable which, likewise, are partly distinguished by a very good fastness to light.

The following table indicates a number of dyestuffsobtainable according to the present process but does not comprise all possibilities for the preparation of dyestufis of very good fastness tolight has the following probable for- 1 iii by using other coupling components and other amines, which components, howevenmust be free fromgroups which would render the dyestufl's soluble in water; it, therefore, is not intended to limit the invention to the dyestuffs mentioned thereini Diazotizing component Coupling component Tint 1(1) 1 amino 4,- math Benzoylaoetic acid Greenish yellow yl 2 nitro benzene anilide (2) 1 amino 4 meth- Benzoylacetic acid- Reddish yellow yl 2 nitro benzene ortho chloranilide j (3) l amino 2.5 di- Benzoylacetic acid- Medium yellow chloro-benzene o'rtho-chloranilide (4) l amino 4- meth- Benzoylaoetic acid- Greeni'sh yellow yl-2-nitro-benzene ortho-chloranilide (5) l amino -4 -chloro- Benzoylacetic acid- Greenish yellow 2-nitro-benzene ortho-cliloranilide 6) 1 amino 2 nitro- Benzoylacetic acid- Medium yellow benzene ortho-cliloranilide v(7) l amino anthra- Benzoylacetic acid Reddish yellow qulnone (8) 1 amino 2 methyM-nitrobenzene ortho-toluidide I Benzoylacetic acid anilide Greenish yellow (9) l amino 2 meth- Benzoylaoetic acid Greenish yellow oxy-i-nitrobenzene an e I p (10) 1 amino 2 nitro- Benzoylacetic acid Reddish yellow 4-inethoxybenzene (ll) 1 amino 4 nitro- 2-methylbenzene anilide Benzoyl acetic acid 7 4 chloro 2 methyl-l-anilide Greenishyellow 4-1nethylbenzene (14) 2.5 dichloro aniline (15) l amino 2 nitroimethoxybenzene zoyl-acetic-acid k methoxy-l-anilide Para methylben zoyl-acetic-acid anaphthylamide Para inethoxyben zoyl acetic acid anillde Reddish yellow Greenish yellow Reddlsh yellow Diasotizing component Coupling component Tint (16) 1 amino 2 nitro- 8 naphtl oyl acetic- Medium yellow l chlorobcnzene acld-anilide 7) l amino 4 nitro- Benzoyl acetic ac d Reddish yellow z-methoxybenzcne dfll'B phenylanile (18) 1 amino 2 metli- Benzoyl-acetic acid- Reddisli yellow yl-t-nitrobenzene ortho-plienylanilide (19) 1 amino 2 meth- Para phenylben Reddisli yellow oxy-4-nitrobenzene izlogl-acetic-acid an- 1 e I (2)) l amino 4 metli- Para-plienylben'zoyl- Reddish yellow oxy-3-nitrobenzene acetic acid anilide We claim:

1. The water-insoluble azo-dyestuffs of the following probable general formula wherein R and R stand for radicals of the henzene-, naphthaleneor diphenyl-series, R stands for a radical oi the benzene-, naphthaleneor anthracene-series, the radicals being free from sul- Ionlc or carboxylic acid groups, dyeing yellow to red shades and being distinguished by their good Iastness properties, particularly by their good fatness to light. p

2. The water-insoluble azo-dyestuffs of the following probable general formula R-OOOHCONHR' i II I I u wherein R and R stand for radicals of the benzene series and R" stands for a radical of the benzene-, naphthaleneor anthracene-series, the radicals being free from sulfonicor carboxylic acid groups, dyeing yellow to red shades and being distinguished by their good fastness properties, particularly by their good fastness to light.

3. The water-insolubleazo-dyestufi of the following probable iormula claim 4.

dyeing a greenish yellow shade and-being distinguished by its good fastness properties, particularly by its good fastness to light.

4. The water-insoluble azo-dyestufi of the following probable formula N as CHi

dyeing a' greenish yellow shade and being distinguished by its good fastness properties, particularly by its good fastness to light.

5. The water-insoluble azo-dyestufi of the following probable formula OOCHCONH Y Q 3 we OCHS I dyeing a greenish yellow shade and being dis- 0 tinguished by its good fastness properties, particularly by its good fastness to light.

6. Fiber dyed with the dyestuffs as claimed in claim 1.

7. Fiber dyed with the dyestuffs as claimed in 5 claim 2.

8. Fiber dyed with the dyestuff as claimed in claim 3.

9. Fiber dyed with the dyestufi' as claimed in V 10. Fiber dyed with the dyestuff as claimed in claim 5. I

FRANZ HENLE. HERBERT KRACKER. 

